1. Field of the Invention
The present invention relates to room temperature curing organopolysiloxane composition effective as a sealing material or a coating material.
2. Description of the Prior Art
Compositions for which curing occurs at normal room temperature through the action of moisture in the air to form a silicone rubber, so-called condensation reaction type room temperature curing silicone rubber compositions, are well known. These compositions are widely used as sealing materials, industrial adhesives and potting materials and the like in a variety of fields including machinery, electrical and electronic devices and architecture and building.
The curing catalyst used in these compositions is typically a tin compound or a titanium compound. However, in the case of tin compounds, various problems arise such as the problem of toxicity, and fragmentation of the backbone chain of organopolysiloxane molecules, leading to cracking and a reduction in the degree of hardness over time. Furthermore, in the case of titanium compounds, different problems arise such as a slow curing time or discoloration.
Furthermore, Japanese Laid-open publication (kokai) No. 2000-129126 (JP2000-129126A) discloses that a bivalent bismuth carboxylate is effective as a curing catalyst for a polyoxyalkylene polymer with a hydrolysable silicon group. However, the curing speed of these compositions is inadequate, and moreover no comment is made in the application of potential application to silicone systems.
Furthermore, bismuth naphthenate has been presented as a possible curing catalyst for room temperature curing organopolysiloxane compositions in U.S. Pat. No. 3,161,614 and U.S. Pat. No. 3,175,993, although no examples are presented, and the polymer systems reported are also different from those described in the present invention.
An object of the present invention is to provide a room temperature curing organopolysiloxane composition which does not use a catalyst based on any of the aforementioned conventional tin or titanium compounds, which exhibits no problems of toxicity, cracking or discoloration and the like, and which moreover cures rapidly, and produces a cured product of good hardness.
In order to achieve the above object, the present invention provides a room temperature curing organopolysiloxane composition comprising:
(A) an organopolysiloxane with at least two hydroxyl groups bonded to silicon atoms within a single molecule,
(B) an organosilicon compound represented by a formula (I) shown below, and/or a partial hydrolysis condensate thereof,
RaSiX4-axe2x80x83xe2x80x83(I)
(wherein, R represents a substituted or unsubstituted monovalent hydrocarbon of 1 to 10 carbon atoms, X represents a hydrolysable group, and a represents an integer of 0 to 3), and
(C) a bismuth compound-based curing catalyst.
As follows is a more detailed description of each of the constituents (A), (B) and (C) of a room temperature curing organopolysiloxane composition according to the present invention.
[Constituent (A)]
An organopolysiloxane of the constituent (A) has at least two hydroxyl groups bonded to silicon atoms within a single molecule, and should preferably have a viscosity at 25xc2x0 C. of 100 to 500,000 mm2/s, and even more preferably from 1,000 to 100,000 mm2/s. Compounds represented by the formula (II) shown below, with hydroxyl groups at both terminals, are particularly suitable.
xe2x80x83HO(R1R2SiO)nHxe2x80x83xe2x80x83(II)
In this formula, R1 and R2 may be the same or different, and represent the same or different substituted or unsubstituted monovalent hydrocarbon groups of 1 to 10 carbon atoms, and preferably 1 to 8 carbon atoms. Suitable examples include alkyl groups such as methyl groups, ethyl groups, propyl groups and butyl groups; cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; as well as groups in which all, or a portion of the hydrogen atoms bonded to carbon atoms within these groups are substituted with a halogen atom or a cyano group or the like, such as chloromethyl groups, trifluoropropyl groups or cyanoethyl groups; and of these, methyl groups and phenyl groups are preferred, and methyl groups are particularly desirable. n represents a number of repeating units which will preferably generate a viscosity at 25xc2x0 C. for the diorganopolysiloxane of 100 to 500,000 mm2/s, and even more preferably from 1,000 to 100,000 mm2/s.
[Constituent (B)]
The constituent (B) is a cross linking agent, and is an organosilicon compound represented by the formula RaSiX4-a, and/or a partial hydrolysis condensate thereof. In the formula, R represents the same or different substituted or unsubstituted monovalent hydrocarbon groups of 1 to 10 carbon atoms, and preferably 1 to 8 carbon atoms. Suitable examples include alkyl groups such as methyl groups, ethyl groups, propyl groups and butyl groups; cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; as well as groups in which all, or a portion of the hydrogen atoms bonded to carbon atoms within these groups are substituted with a halogen atom or a cyano group or the like, such as chloromethyl groups, trifluoropropyl groups, or cyanoethyl groups; and of these, methyl groups, ethyl groups, vinyl groups and phenyl groups are preferred. a represents an integer of 0 to 3.
X is a hydrolysable group, and suitable examples include alkoxy groups, ketooxime groups, 1-methylvinyloxy groups and acetoxy groups and the like, although of these, alkoxy groups, ketooxime groups and acetoxy groups are preferred, and alkoxy groups are particularly desirable.
In those cases in which X is a ketooxime group, specific examples of the constituent (B) include silane compounds such as methyltris(diethylketooxime)silane, methyltris(methylethylketooxime)silane, vinyltris(methylethylketooxime)silane and phenyltris(diethylketooxime)silane, or partial hydrolysis condensates thereof.
In those cases in which X is an alkoxy group, specific examples of the constituent (B) include silane compounds such as trimethoxymethylsilane, trimethoxyphenylsilane, trimethoxyvinylsilane, triethoxymethylsilane, triethoxyphenylsilane, triethoxyvinylsilane and tetramethoxysilane, or partial hydrolysis condensates thereof.
These compounds may be used singularly, or in combinations of two or more compounds.
The quantity of the constituent (B) used is preferably 1 to 30 parts by weight, and even more preferably 3 to 20 parts by weight per 100 parts by weight of the constituent (A). At quantities less than 1 part by weight the stability of the composition deteriorates, and the composition may gel during storage, whereas if the quantity exceeds 30 parts by weight, the curing shrinkage becomes overly large and the physical properties of the cured product deteriorate.
[Constituent (C)]
The bismuth compound-based curing catalyst of the constituent (C) is a particularly important constituent of a room temperature curing composition according to the present invention.
There are no particular restrictions on the bismuth compound-based curing catalyst of the constituent (C), provided it acts as a catalyst for the condensation reaction between the constituent (A) and the constituent (B), although organic bismuth compounds are preferred, and bismuth carboxylates are particularly preferred. Of these, trivalent bismuth carboxylates are particularly preferred, as represented by the general formula (III) shown below.
(R3CO2)(R4CO2)(R5CO2)Bixe2x80x83xe2x80x83(III)
(wherein, R3, R4 and R5 may be the same or different, and represent a saturated or unsaturated hydrocarbon group of 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms.)
Of these compounds, straight chain or branched chain alkyl-based carboxylates of trivalent bismuth are particularly preferred, and by using these compounds, compositions with particularly superior curability can be achieved.
Specific examples of these bismuth compounds are presented below:
(CH3CO2)3Bi, (C2H5CO2)3Bi, (C7H15CO2)3Bi, (C9H19CO2)3Bi, (C3H7CO2)3Bi, (C4H9CO2)3Bi, (C5H11CO2)3Bi, (C6H13CO2)3Bi, (C6H13CO2)3Bi, (CH3CO2) (C7H15CO2)2Bi, and (C7H15CO2) (C9H19CO2)2Bi.
The constituent (C) must be present in a sufficient quantity to act as an effective catalyst, and specifically, quantities of 0.01 to 20 parts by weight, and preferably 0.1 to 10 parts by weight are required per 100 parts by weight of the constituent (A).
[Other Constituents]
Where necessary, constituents other than the aforementioned constituent (A) to (C) may be added to a composition of the present invention, provided such addition does not impair the properties of the composition such as the curability, and the resistance to cracking and discoloration.
Examples of other constituents include fibrous materials such as asbestos, glass fiber, carbon fiber and organic fibers, fillers such as silica, talc, carbon black, bentonite, calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide and celite, network polyorganosiloxane resins formed from triorganosiloxane units and SiO2 units, heat resistance enhancing agents or cold resistance enhancing agents such as red iron oxide and cerium oxide, waterproofing agents, rust proofing agents, antibacterial agents, mold proofing agents, plasticizers, coloring agents, and fire resistance imparting agents. In addition, the various carbon functional silanes may also be added to improve adhesion.
In particular, the addition of silica and/or calcium carbonate as a filler is desirable. Silica may be either fumed silica or precipitated silica, although fumed silica is preferred, and silica which has undergone hydrophobic surface treatment is particularly preferred. Either untreated calcium carbonate or calcium carbonate which has undergone hydrophobic surface treatment may be used.
The quantity of the filler should be from 1 to 200 parts by weight, and preferably from 3 to 100 parts by weight per 100 parts by weight of the organopolysiloxane of the constituent (A).